Erica Pensini

Fundamental Study of Emulsions Stabilized by Soft and Rigid Particles

Two distinct uniform hybrid particles, with similar hydrodynamic diameters and comparable zeta potentials, were prepared by copolymerizing N-isopropylacrylamide (NIPAM) and styrene. These particles differed in their styrene to NIPAM (S/N) mass ratios of 1 and 8 and are referred to as S/N 1 and S/N 8, respectively. Particle S/N 1 exhibited a typical behavior of soft particles; that is, the particles shrank in bulk aqueous solutions when the temperature was increased. As a result, S/N 1 particles were interfacially active. In contrast, particle S/N 8 appeared to be rigid in response to temperature changes. In this case, the particles showed a negligible interfacial activity. Interfacial shear rheology tests revealed the increased rigidity of the particle-stabilized film formed at the heptane-water interface by S/N 1 than S/N 8 particles. As a result, S/N 1 particles were shown to be better emulsion stabilizers and emulsify a larger amount of heptane, as compared with S/N 8 particles. The current investigation confirmed a better performance of emulsion stabilization by soft particles (S/N 1) than by rigid particles (S/N 8), reinforcing the importance of controlling softness or deformability of particles for the purpose of stabilizing emulsions.

Carboxymethyl cellulose binding to mineral substrates: Characterization by atomic force microscopy-based Force spectroscopy and quartz-crystal microbalance with dissipation monitoring

The attachment of the sodium salt of carboxymethyl cellulose (CMC) onto iron oxide and various silicate substrates in aqueous solution as a function of salt concentration and pH was studied by atomic force microscopy-based force spectroscopy (AFM) and quartz-crystal microbalance with dissipation monitoring (QCM-D). Both ionic strength and cation valency were found to influence substrate binding. Notably, QCM-D experiments strongly suggested that the solubility of CMC is directly impacted by the presence of CaCl2. Such data are critical for the design of new molecules for stabilizing mineral floc dispersions and for assessing the mobility of CMC-coated particles in the subsurface. Modeling of AFM data with an extended Ohshima theory showed that van der Waals and steric forces played a major role in the interactions between CMC and mineral substrates, and that hydration forces were also important.

Forces of interactions between bare and polymer-coated iron and silica: effect of pH, ionic strength, and humic acids.

The interactions between a silica substrate and iron particles were investigated using atomic force microscopy-based force spectroscopy (AFM). The micrometer- and nanosized iron particles employed were either bare or coated with carboxymethyl cellulose (CMC), a polymer utilized to stabilize iron particle suspensions. The effect of water chemistry on the forces of interaction was probed by varying ionic strength (with 100 mM NaCl and 100 mM CaCl₂) or pH (4, 5.5, and 8) or by introducing 10 mg/L of humic acids (HA). When particles were uncoated, the forces upon approach between silica and iron were attractive at pH 4 and 5.5 and in 100 mM CaCl₂ at pH 8, but they were negligible in 100 mM NaCl buffered to pH 8 and repulsive in water buffered to pH 8 and in HA solutions. HA produced electrosteric repulsion between iron particles and silica, likely due to its sorption to iron particles. HA sorption to silica was excluded on the basis of experiments conducted with a quartz-crystal microbalance with dissipation monitoring. Repulsion with CMC-coated iron was attributed to electrosteric forces, which were damped at high ionic strength. An extended DLVO model and a modified version of Ohshimas theory were successfully utilized to model AFM data.

Effect of Water Chemistry and Aging on Iron—Mica Interaction Forces: Implications for Iron Particle Transport

The transport of particles through groundwater systems is governed by a complex interplay of mechanical and chemical forces that are ultimately responsible for binding to geological substrates. To understand these forces in the context of zero valent iron particles used in the remediation of groundwater, atomic force microscopy (AFM)-based force spectroscopy was employed to characterize the interactions between AFM tips modified with either carbonyl iron particles (CIP) or electrodeposited Fe as a function of counterion valency, temperature, particle morphology, and age. The measured interaction forces were always attractive for both fresh and aged CIP and electrodeposited iron, except in 100 mM NaCl, as a consequence of electrostatic attraction between the negatively charged mica and positively charged iron. In 100 mM NaCl, repulsive hydration forces appeared to dominate. Good agreement was found between the experimental data and predictions based on the extended DLVO (XDLVO) theory. The effect of aging on iron particle composition and morphology was assessed by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS) revealing that the aged particles comprising a zero valent iron core passivated by a mixture of iron oxides and hydroxides. Force spectroscopy showed that aging caused variations in the adhesive force due to the changes in particle morphology and contact area.

Forces of interactions between iron and aluminum silicates: Effect of water chemistry and polymer coatings

Atomic force microscopy-based force spectroscopy (AFM) was employed to investigate the forces of interaction between aluminum silicates (mica and a synthetic aluminum-silicate) and iron particles, both bare and coated with carboxymethyl cellulose (CMC) polymer. Experiments were conducted in water and salt solutions (100mM NaCl and 100mM CaCl2) at pH 5.5, in water at pH 4 and 8, and in 10mg/l humic acid solutions. In addition, humic acid sorption onto the synthetic aluminum-silicate was probed with a quartz crystal microbalance with dissipation monitoring (QCM-D). Interactions between bare iron particles and aluminum silicate were attractive except at pH 8 and in the presence of humic acids in which case forces upon approach were repulsive. Interactions between bare iron and mica were similar, except that repulsive forces upon approach were measured in 100mM NaCl solutions, possibly due to increased hydration of mica compared to aluminum silicate. Interactions between CMC coated iron particles and aluminum-silicates were either repulsive or at most weakly attractive, likely due to repulsive electro-steric forces associated with the CMC. QCM-D results indicated that humic acids adsorbed to aluminum silicate, producing electro-steric repulsion to coated and uncoated iron. AFM data were successfully modeled using extended DLVO theory and a modified Ohshimas model. This modeling provided insights into the contributions of various processes to the measured interaction forces, highlighting the importance of van der Waals and hydration forces.